Treatment of materials to impart antistatic properties and products



United States PatentO TREATMENT OF MATERIALS TO IMPART ANTI- STATIC PROPERTIES AND PRODUCTS Arnold H. Gruber, Stamford, Conn., and William J. van Loo, Jr., Rye, N. Y., assignors to Amen'can Cyanamid Company, New York, N. .Y., a corporation of Maine No Drawing. Application April 9, 1954 Serial No. 422,262

16 Claims. (Cl. 117-1383) This invention relates broadly to the antistatic treatment of materials and to the products thereof. More particularly the invention relates to the method of conditioning a material or article which, in a dry state, nor mally tends to accumulate static charges of electricity thereon, whereby this tendency is minimized or obviated, and to the treated materials or articles, for instance, textile materials in fiber, fabric or other form, sheet materials, e. g., those used in making photographic films, etc. The scope of the invention includes molding compositions and molded articles comprising (1) a plastic material (e. g., a vinyl resin) which normally tends to accumulate static charges of electricity after the article has been molded (or during molding) and (2) 'an antistatic agent therefor comprising a particular nitrogenous compound or compounds.

The nitrogenous compounds'that are used in the compositions and articles of this invention can be represented by the general formula wherein R represents a member of the group consisting of aliphatic hydrocarbon and alicyclic hydrocarbon radicals containing at least 7 carbon atoms, R designates a radical represented by the formula (C,,H ,,O),,,H where n represents a positive integer from 2 to 4, inclusive, and m is a positive integer and is at least 6 (e. g., from 6 to 200 or more and advantageously from 6 or 7 to about 60 or 70), R" represents a member of the group consisting of alkyl and hydroxyalkyl radicals containing ice ions (that is, Y can represent a chloride, bromide, fluoride or iodide), sulfate, sulfonate, phosphate, phosphite, hydroxide, borate, carbonate, hydrocarbonate, thiocyanate isocyanate, sulfite, bisulfite, nitrate, nitrite, oxalate, silicate, sulfide, cyanate, acetate ethylsulfate and the other common inorganic and organic ions.

The nitrogenous compounds embraced by Formula I are sometimes generically termed herein as quaternary ammonium compounds, which term, when R" represents hydrogen, includes compounds that are usually designated as tertiary amine salts.

. has associated therewith from, by weight, 0.2% to 15% frorirl to 5 carbon atoms, inclusive, and radicals having the same meaning as R, R represents a memberv of the group consisting of hydrogen and radicals having the same meaning as R, and Y represents an anion.

Illustrative examples of radicals represented by R in Formula I are heptyl, octyl, octenyl, nonyl, nonenyl, decyl, decenyl, undecyl, undecenyl, tridecyl tetradecyl, tetradecenyl, heptadecyl, heptadecenyl, octadecyl, octadecenyl the residue of abietic acid, etc. Illustrative examples of radicals represented by R are hexaetheneoxy, heptapropeneoxy, octaisopropeneoxy, hexabuteneoxy, heptaisobuteneoxy, octaetheneoxy, decabuteneoxy, octadecaetheneoxy, eicosaisopropeneoxy, triacontaetheneoxy, octatriacontaetheneoxy, etc. Illustrative examples of radicals represented by R" and R' are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-amyl, isoamyl, see-amyl, tert.-amyl and the other isomeric amyl radicals hydroxyethyl, hydroxypropyl, hydroxyisopropyl, dihydroxypropyl, hydroxybutyl, dihydroxybutyl, hydroxyamyl, dihydroxyamyl, etc. Illustrative examples'of anions represented by Y are the halide butyrate, celluloseformate, cellulose propionate, cellulose of the aforesaid nitrogenous compound, based on the weight of the dry, untreated material. The nitrogenous compound is dissolved or dispersed (dispersed being used generically herein to cover both solutions and dispersions) in a volatile liquid, e. g., water, alcohol (for instance isopropanol) or a mixture of water and alcohol. The treated material or article is then dried to volatilize the aforesaid liquid.

As has been indicated hereinbefore another embodiment of the present invention is directed to the production of molding compositions and molded articles. Such compositions and articles are produced by incorporating the antistatic agent comprising a nitrogenous compound of the kind embraced by Formula I into a molding composition containing a plastic material which normally tends to accumulate static charges of electricity after the article has been molded, and then molding the re sulting molding composition. In such applications the amount of the said nitrogenous compound which is incorporated into the molding composition generally constitutes, by weight, from 1% to 15% of the weight of the said plastic material. It was known before this invention to use quaternary ammonium compounds of akind different from those which are used in practicing the present invention as antistatic agents for materials that normally tend to ac; cumulate static charges of electricity, and specifically a thermoplastic vinyl resin. In this connection see, for example, Carnes Patents 2,626,876 and 2,626,877, dated January 27, 1953.. V

The'present invention is based on the discovery that nitrogenous compounds of the kind embraced by Formula I possess an unobvious combination of properties which renders them eminently suitable for the treatment of a wide variety of textile materials, e. g., in the form of continuous-filament yarn, staple fiber, tow, roving, knitted, woven or felted fabrics, and which may be 'cornposed of or contain fibers or filaments of wool, silk, cellulose esters (e. g., cellulose acetate, cellulose acetobutyrate, etc.), cellulose ethers (e. g., ethyl cellulose, benzyl cellulose, etc.), viscose rayons, nylon, thermoplastic vinyl resins (e. g., vinyl chloride polymers and copolymers, acrylonitrile polymers and copolymers, etc.), and other natural and synthetic textiles in fiber, fabric or other form. The preferred compositions employed in practicing this invention have both a softening and lubricating action on the textile and, in addition, have the ability to retard or obviate the accumulation of static charges of electricity on such textiles which nor- I rhally tend to become charged with static electricity.

Furthermore, the preferred antistatic .compositionsare relatively durable in their antistatic efiect, especially on certainarticles (e, g., polyacrylonitrile fibers); that is,

they impart antistatic properties to the material which has been treated with the composition through a series of launderings', more particularly through more than 5 launderings under the conditions described'la ter herein.- In addition, the preferred antistatic agents employed in practicing the present' invention are' substantive under the preferred conditions. of application (namely, at or near the boil) to certain particular materials, e. 3., polyacrylonitrile fibers; that is,.they exhaust the bath used in applying them to the .rnateria l and become :fixed V thereon in the same mannerthat certain, dyes are/substantive, to a material beingLdyedjandb'ecome fixedion thejnaterial'vvithout theruse of a inordant.

"In many types'of mblded article'sgthe' plastic" material contained'thefein is one "which normally tends to ,ac-

eumulate static charges of electricity. This 'is particularly objectionablelto the retailer 1 since itinecessita'tes fre quentlwiping of the article to remove the dust, and this in' turn're'sultsina'further. accumulation of a static charge. The matter vot atxzumulated static electricity on the article also is veryobjectio'nable to the housewife in the case of'decorative and other household articles since" the accumulated 1 static electricity attracts dust particles and necessitatesmore frequent dusting. (wiping to: remove dust) and cleaning of the articles. With other molded articles such, for example, as sound-reproducing records and specifically phonograph records, the dust particles attracted by'the accumulated static electricity constitute a more serious practical objection since they-cause surface noise and abrasion of the record and hence are one cause of poorftonal or reproduction qualities and shortlife of 'the record. Attempts to solve this problem by surface treatment 'of the molded article with an antistatic agent have not been commercially successful since the treatment islexpen'sive and involves an extra step or steps; also, it imparts,at best, only temporary. antistatic characteristics to the treated article.

Furthermore, in the case of phonograph records, such a surface treatment often detracts from the tonal. and reproduction qualities of the record.

Q Foroptimum'res'ults, the antistaticiagentshould be compatiblewvith, or substantiallyruniformly dispersible throughout, the plastic material. Also it should not bleedfrom the molded article; should notdetract from the moldability of the molding composition; and should not impart objectionable characteristics to the molded article, e. g., decreasetheyresistance towear and handling, or, inthecase of sound records, lessenthe tonal reprokind embraced by Formula l would retain their antistatic properties after being subjected to the. heat incurred during molding of the plastic containing the antistatic agent. r

PREPARATION OF NITROGENOUSCOMPOUND The nitrogenous compounds used as antistatic agents in practicing the present invention. can be prepared by various methods, for instance as is'full'y described in the copending application of Walter Schullerand Joseph 1. Games, Serial- No. 422,243, filed concurrently herewith, and now abandoned- Thus, some of the'com pounds advantageously can, he prepared by a reaction illustrated by the following equations and wherein ethylene oxide is shown as the alyklene oxide employed:

(H) n I The reaction is carried out in a reaction-vessel fitted with-a mechanical stirrer, a DryJce reflux condenser, a

duction characteristics orvthe faithfulness ofr'eproduction," or shorten the normal life of the sound tracks.

The preent invention is based on the further discovery that an antistatic agent comprising a'nitrogenous con-l pound of the kind embraced by Formula I, .or mixture thereof in any proportions, ,can be substantially hornegen cously dispersed or distributed throughout, a moldng composition containing a plastic'material 'which'normally ;tends to accumulate static chargesof electricity,

with or without fillers 'or other additives commonly incorporated into molding compositions,1'and that the resultmg composition can be'moldedintoarticles of manufacture, specifically sound records, having antistatic characteristics, throughout the normal useful life of the article and without detracting in any Way from its other The quaternary ammonium salt is dissolved .in'iwater for a water-tertiary alcoholmixture and the solution-jadjusted to pH 8 by the addition 0f' 40%- aqueonssodinrn useful properties. In many cases the antistatic characteristics are substantially permanent, 'as evidenced by the fact that the article retains-it's antistatic properties even after, repeated washings with soap and water.

have been predicted; One reason for this inability to predict the results obtained is because it could nothave been predicted-that the nitrogenous compounds *ofthe V V This was quite surprising and unexpected and in no way could basic. The resulting solution (pH ofaboutS) is heated V to reflux (80400 0.)," and ethylene oxide is added at sucha rate that moderate reflux takes place. After the desired amount-ofiethlene oxide has been addedover: 5

period; of from 2101 10 hours; the reaction rnixture is refluxed for an additional; hour to insure. that the peso:

tion has gone to completion: VA potentiometrie titration.

is carried out at this point'to makecertain that the quaternariza'tion is "complete; then adjusted: to, a suitable pH; e. -g.,.a 5, with ,theappropriate-acidr Another method by which some of thecornpounds'ade r us v c n b iprep d sb ix a t e us by the ;following;.equationandwherein ethylene oxide again is shown as the alkylene-oiiide employed;

hydroxide. 'Anadditional' 15 mole percent of sodium hydroxide (hased on the quaternary ammoniumsaltyis added, again as a 4 0% aqueous solution. ."The mixture is heated to-reflux and ethylene'oxide introduced below the surface of theliquid at sucha rate that ai moderate amount of reflux, at a reflux temperature, between -1007 C., is obtained. I The reaction is carried-out in [The alkalinefiolution is V ruleru 7e s a reaction vessel fitted with a mechanical stirrer, a Dry- Ice'reflux condenser, a thermometer and a source of heat such as a steam bath. After the desired quantity of ethylene oxide has been added over a period of from two to ten hours, the reaction mixture is refluxed for an additional one to two hours (temperature at 95105 C.) to insure the completeness of the reaction. The resulting solution is adjusted to a suitable pH, e. g., a pH of about 4 or 5, by the addition of the appropriate acid.

The free quaternary ammonium base can be prepared from any of the hereindescribed quaternary ammonium salts of inorganic acids by treating a water-free solution of the salt, for instance the chloride, in n-butanol (or isopropanol or tert.-butanol) with a slight excess of the sodium salt of the alcohol used. After cooling and standing for about 16 hours, the crystalline sodium salt of the inorganic acid is filtered from the solution of quaternary ammonium alkoxide. Water is added to the mixture to yield the quaternary ammonium hydroxide.

The reaction is illustrated by the following equations:

(Iv) (omomoynn R-C O-NH-(CHnla-i -R" ,o1- otmoNa (omommmH HO RCO-NH(CH:):N-B ,0C4HB+N8C1 (CHzCHaOh-H n-c O-NH-(CHzh-MB ,on canon More detailed procedures for preparing certain specific compounds are given in some of the examples given later herein.

PRODUCTION OF MOLDING COMPOSITIONS This invention is applicable to the production of molding compositions comprising any plastic (i. e., moldable plastic) material which normally tends to accumulate static charges of electricity after the article has been molded and among which are included, in addition to vinyl resins, such plastic (both thermoplastic and thermosetting) materials as the following: nylon, polyethylene, ethyl cellulose, cellulose acetate, cellulose butyrate, cellulose nitrate, polyester resins, phenolic resins, modified and unmodified alkyd resins, ureaformaldehyde resins, melamine-formaldehyde resins, etc.

The present invention is particularly applicable to the production of molding compositions and molded articles, especially phonograph records, containing a vinyl resin, more particularly a thermoplastic vinyl resin, e. g., polystyrene; polyvinyl chloride; copolymers of vinyl chloride and vinylidene chloride, especially those containing from about 5% to about by weight of vinylidene chloride combined in the copolymer molecule; and copolymers of vinyl chloride and vinyl acetate, especially those containing from about 6% to about 15% by Weight of vinyl acetate combined in the copolymer molecule. Other examples include resins produced by the conjoint polymerization of a vinyl halide, e. g., vinyl chloride, with a nitrile of an unsaturated acid, e. g., acrylonitrile, methacrylonitrile, etc.; resins produced by the halogenation (e. g., chlorination) of polyvinyl chloride and other polyvinyl halides; resins produced by the chlorination of copolymers of a vinyl halide with a vinyl ester of an aliphatic acid; resins produced by the conjoint polymerization of vinyl chloride or other vinyl halide with an N-alkylated imide derivative of an aliphatic acid, e. g., N-butyl maleimide; and resins produced by the conjoint polymerization of a vinyl halide, a vinyl ester of an aliphatic acid and maleic acid. Copolymers of a vinyl halide and a vinyl ester of an aliphatic acid other than the vinyl chloridevinyl acetate copolymers described above can be used in the molding compositions and molded articles of this B invention. Such resinous copolymers are more fully described in, for example, Rugeley et a1. U. S. Patent No. 2,161,766, and generally contain about 50% to about by weight of combined vinyl halide in the copolymer, the remainder being a vinyl ester of an aliphatic acid.

In practicing the embodiment of this invention directed to the production of molding compositions, a suitable amount of an antistatic agent comprising a nitrogenous compound of the kind embraced by Formula I is incorporated by suitable means into the plastic material to form a substantially homogeneous composition. Fillers and/ or other additives normally employed in the preparation of'the composition may also be incorporated therein, as desired or as conditions may require. The amount of antistatic agent which is employed may be considerably varied, but in molding applications is generally within the range of from about 1% to about 15%, more particularly from about 2% to about 10%, by weight of the vinyl resin or other plastic material used.

Taking the production of a vinyl-resin type phonograph record as illustrative of the molded article to be made, the following is a typical general procedure. The vinyl resin and antistatic agent, together with the usual fillers and other additives (e. g., carbon black, stabilizer, mineral filler, etc.) are blended together in conventional ap paratus, e. g., a ribbon blender, until a substantially uniform mixture has been obtained. Since the antistatic agent is normally prepared and made available in the form of an aqueous or aqueous-alcoholic solution or dispersion, non-uniform distribution may occur in this blending step unless care be taken to avoid the same. A nonuniform blend at this stage would lead to trouble in the fusion step. This possible source of trouble can readily and conveniently be avoided by first depositing the antistatic agent on the surfaces of one of the other ingredients that is to be incorporated into the molding composition. The amount of antistatic agent which is deposited on the surfaces of the finely divided or comminuted filler or additive, when this practice is followed, may be varied as desired or as conditions may require. Ordinarily, however, the amount of antistatic agent which is deposited on the surfaces of the filler material will constitute from about 0.05% to about 300% or more by weight of the filler. Depending, for example, upon the particular kind of filler which is treated and the mode of treatment, the antistatic agent may be deposited mainly or almost solely on the external surfaces of the filler, or, in the case of porous fillers, on both internal and external surfaces of particles of the filler. The amount of antistatic agent on thefiller should not be so great as to cause'the treated filler to be so cohesive that it loses its normally free-flowing characteristics. Conveniently the antistatic agent is applied to the tiller in such concentration that use of the treated filler in its desired percentage in the? ultimate composition will result in a final composition containing the desired amount of antistatic agent.

The deposition of the antistatic agent upon the surfaces of one of the other additives to the molding composition maybe effected by any suitable means. One suitable method comprises flooding one of the powdery additives, e. g., carbon black, mineral filler (e. g., finely divided calcium carbonate), vinyl resin, etc., with the amount of antistatic agent to be incorporated in the molding composition and which has been diluted with water or other volatile liquid medium to give a uniform slurry, after which the mixture is dried to its original powdery form.

Fusion of the blended mixture is normally done in a heated internal mixer, e. g., a Banbury mixer. After the fusion of the plastic material with the additives, the charge is dumped and sheeted out on a mill. From the resulting slab or sheet, pieces are then cut of a size so that each blank or biscuit will make a record.

' 7 To mold the record, the biscuit. is preferably preheated and then placed between the stam'persin the presswhich is warm. .Atter closing, thepressis cooled; .and at a suitable stage in the cooling cycle the press is'lopened and the: record removed. a t

ANTISTATIC TREATMENTOF SHAPED ARTICLES In using the antistatic ,compositionsherein involved in the treatmentjof shaped or fabricatedarticles which, in a. dry state, normally have a tendency to accumulate static-charges of electricity, a solution or a dispersion of thecomposition is applied by any suitable means, to the obtained when the antistatic agentis applied at the boiling article, followedby drying ot' the treated article .to vola- 1 tilize the solvent or liquid component. The treatment is.,.applicable to such articles, in various forms, for in- I stance inthe form of filaments, fibers, yarns, film's, woven, knitted and felted fabrics, etc. Tnese antistatic compositions are particularly useful as antistatic finishes for fibers or fabrics'composed of or comprising substantial proportions of silk, nylon, wool, V viscose ,rayons,

' cellulose acetate or other cellulose ester rayons, vinyl resins, including homopolymeric and copolyrnericacrylonitrileand therthermoplastic vinyl resins.-

7 Asia well known to those skilled' in the art, the vinyl resins constitute a' class of materials which develop or,

tend develop an electrostatic charge upon their surfaces-when-fihers or other articles made therefrom are subjected toiriction during theirproductionand during processing or fabrication of the fibers intofabric or other The antistatic compositions involved herein have been articles, as well as during the use of the finished article.

filaments, fibers, yarns, films and other shaped articles 7 composed of or. containinga vinyl resin so as to obviate or minimize their tendencyto accumulate static charges c rdamo Numerousexamples of such vinyl resins have been given hereinbefore, One preferred class of Antistatic compositions used in practicing the present invention: may be applied under various pH. conditions,

as desired or as. conditions may require. They may be used alone or with other additives or'modifiers, e. g.,

mono-, diand triethanolamines, lanolin, morpholine, di-

sodium phosphates, dialltyl phosphates,'allryl esters. of longgchain fatty acids, e. g. the ethyl to amyl, inclusive, esters of, fatty acids containing from 12, to 18 carbon atoms, inclusive, conventional wetting and/or-dispersing agents,;silicone oils,:mineral, vegetable and animal oils,

able amount of the antistatic composition but ordinarily it constitutes from about 0.1%- ,toabout, 20% by weight thereof. The dispersion may be applied, for example,

by immersing the fiber (or, other shaped article. formed of vinyl resin or other material), in the dispersion, orby spraying, padding, brushing or otherwise contactingfthearticle with the dispersion. The dispersion may be applied at temperatures ranging, for instance, from room.v temperature (20-30 C.) up to the boiling temperature of thedisper'sion, e, g., about 100 'C., as desired or 'as conditions. may require. Optimum .results generally'are 7 temperature of the dispersion (or at a higher temperature under pressure) and an immersion time of, for, example,

from lO minutes: to 1 hour. Upon drying the fib er or, a

other shaped article at room temperature or at an elevated temperature, e.. g., on heated'drying rolls, in ovens; tunnel, driers, etc., the;treated article hasthe solid antistatic composition deposited at least on the outer'surfaces there; a

of. The amount. of antistatic composition which is present in or on the dried, treated material or article may vary considerably, but ordinarily it is present therein or-thereon in an amount, by weight, corresponding to fror'rrahout 0.2% to about 15% of the dried, untreated article.

The antistatic compositions employed in practicing this inve'ntionmaybe applied to, for instance, a shaped the;-

moplasticviriyl resin, for example, yarns of associated filamentsof such a resin, in" the course of the production foundto be. particularly adapted for use in conditioning etc. The liquid compositions can. be applied ,advanta- V composition imparts antistatic characterisitcs to the fiber geously many cases at a pH of about 6.0 to 7.0, e. g.,

to'articles. formed of a polymerof acrylonitrile' or other J vinyl resin, or. to. other materials requiring an' a'ntistatic treatment. e

I Theiantistatic compositions with the use of which this invention is. concerned not only are capable of imparting antistatic, characteristics to vinyl resins (including thermoplastic vinyl resins) iand other articles which normally,

7 wliendry, have a tendency to accumulate electrostatic charges but in general they are also able to effect this result without detrimentally affecting the color, tensile strength,jelasticity, chemical resistance, bacterial, and

fungal resistance, and other valuable properties of the ferred'antistatic compositions also-beneficially afiectthe' article by-imparting softness and lubricity thereto. 7

The antistatic compositions herein involved are preferably applied to the article tobetreated in the-form of a liquid dispersion; This dispersion may contain any suitof the yarn or other shaped article, or subsequent to the production of the yarn and beioreor aiter any textile operations in which suchyarns are used, especially those operations which include or involve a winding operation.

By applying the antistatic'compositionin the'course of producing the filaments or fibers, the application may suffice for subsequent textile operations. If desired, how

ever, the textile-treating agent comprising the antistatic" composition may be applied both during the process of producing the yarns as well as later when these yarns are fabricated into textile fabrics.

The antistatic composition also may be applied to, for

' instance, thermoplastic vinyl resins or otherarticles when the latter are in gelled form. For'example, a liquidtreating agent containingthe antistatic composition may beapplied to a fiber in gel state, more particularly an aquagel state, and in which the solid phase comprises, 7 for" example, an acrylonitrile polymerization. product,

7 more particularly such a product which contains' in the i molecules thereof an'a verag'e of at least-about by 7 weight of combined acrylonitrile; Thereafterthe'thusly treated, gelled fiber is dried, for example by continuously passing the fiber over heated drying rolls as is described more 'fully in, for instance, Cresswell et al. PatentiNo. 2,558,733, dated July 3, 1951. In this way the applied both during and after drying thereof. {The-antistatic compositions herein involved are'espe- 'cially' suitable for use in the treatment of orientedor unoriented fibers, films, etc., in gelstate and which have been produced as described in, forexample, Cresswell Patents 2,558,730 and 2,558,731 date-dluly 3, 1951, and. in the aforementioned Cresswell et al. Patent N0...

2,558,733; also, in the treatment of the dried products, whereby the tendency of the dried material to accumulate static charges of electricity is obviated or minimized and a treated material which, in general, issofter to the touch is obtained. 7

'As has been mentionedhereinbefora; any suitable method may be employed in applying the antistatic com cated article and prior to or during its 'ser iceuse. For

example, if; the: conditioning agent comp'risingthe anti; static composition is to beapplied to the yarn after spin- 9 ning, the yarn may be brought into contact with a wick, roll or felt which has been wetted with a solution or dispersion containing the antistatic agent dissolved or dispersed in water, ethanol (or other alcohol), a wateralcohol mixture, or other liquid solvent or dispersion media. Alternatively, the antistatic composition in liquid state may be applied by immersing the article in a bath containing the same. Examples of points during the production of a yarn at which the antistatic composition may be applied are during stretching of a wet-spun yarn or fiber to orient the molecules thereof, or between any of the guides or godets or other rolls employed in the spinning process, or between the guide and the point of winding and/or twisting; or, the antistatic composition may be applied after windin onto cones, spools, bobbins or the like; or, in the case of staple fiber manufacture either prior to or after cutting the tow into staple lengths.

For example, a tow of filaments that is to be cut into staple fibers may be treated with a dispersion of the antistatic composition prior to cutting. Alternatively, staple fibers such as those which may occur naturally or those out from continuous lengths of natural or artificial filaments, may be treated with a dispersion of the antistatic composition, e. g., by spraying while the fibers are being moved on a continuous conveyor beneath the spray, followed by drying the treated fibers. Or, the treatment may be applied during an intermediate stage of the spinning operations, e. g., immediately after lapping, carding, drawing or slubbing; or, the antistatic composition may be applied during fiber-mixing or -blending operations.

If desired, the antistatic composition which is deposited .in or on the treated article may be allowed to remain in place during and after the production of the article in its ultimate form. The treated fibers or fabrics can be dyed, if desired, without scouring off the antistatic finish prior to dyeing.

The use of nitrogenous compounds of the kind embraced by Formula I in the treatment of, for example, wool, nylon, silk, viscose and acetate rayons, vinyl resins, etc., to obviate or lessen the tendency of such materials to accumulate charges of electricity thereon has numerous advantages, among which may be mentioned their ease of application (e. g., as aqueous dispersions, at any pH, in the cold, or warm, or at the boil); the fact that they are chemically stable to aging; the fact that they do not form insoluble compounds or bodies in dispersions thereof in hard water; their effectiveness both as antistatic agents and in lubricating and softening the shaped article in yarn or other form, whereby the treated yarn, film or other article is rendered more amenable to further processing or fabricating (e. g., weaving, knitting, etc., in the case of yarns); the fact that they do not physically damage or have any other deleterious efifect upon the fiber, fabric or other article to which it has been applied or in which it is incorporated; their compatibility with other conditioning agents commonly employed in finishing compositions used in treating fibers and other shaped articles; their case of removal from the treated article, when such removal appears to be desirable for subsequent processing or use of the article; their non-harmful effect upon the vinyl resin or other material which is subjected to treatment; and the substantivity and antistatic durability that is obtained with the preferred antistatic agents on certain articles, e. g., polyacrylonitrile fibers.

The term yarn as used generically herein includes within its meaning a single filament, a plurality of filaments associated into the form of a thread and which may be of any desired twist, single or multiple threads associated or twisted together, as well as staple fibers produced from filaments or threads and spun yarn produced from such staple fibers. The term fiber as used generically herein includes both moncfilaments and multifilaments.

In order that those skilled in the art may better understand how the present invention can he carried into 10 efiect, the following examples are given by way of il11istration and not by way of limitation. All parts and percentages are by weight.

The first eight examples are illustrative of the use of the antistatic agents with which this invention is concerned in the production of molding compositions and molded articles.

Example 1 In this example blending is done by hand-stirring the contents of a vessel with a fiat-blade stirrer. The fusing cycle is carried out on a two-roll mill, with both rolls at C. The molding operation consists in forming a piece 3" x 3" x 0.1 in a test-sheet mold. The blanks are formed between sheets of aluminum foil to facilitate removal from the mold. Antistatic properties are determined by rubbing the surface of the blank 40 times with a woolen cloth and immediately thereafter passing the rubbed blank about Adabove a bed of finely divided cigarette ashes. A sample having no antistatic characteristics will be completely covered with ash. A sample exhibiting excellent antistatic properties will show no pick-up of ashes.

Vlnylite VYHH resin 1 Carbon black Dibasic lead stearate (stabilizer) Gamma-caprylamidopropyl diethyl hexaethenoxy ammonium chloride Gamma-lauramidopropyl dipropyl nonaetheneoxy ammonium bromide Carbon black pretreated with gamma-steeramidopropyl di-(fi-hydroxyethyl) octaetheneoxy ammonium phosphate in a weight ratio of 2 parts of carbon black to 1 part of the quaternary ammonium salt 1 A copolyruer of vinyl chloride and vinyl acetate having 12-15% of vinyl acetate combined in the copolymer molecule.

Blanks molded from the above molding compositions show excellent antistatic characteristics.

Example 2 The procedure is the same as described under Example 1, and the molded articles have excellent antistatic characteristics.

Example 3 An aqueous solution containing 10% of abietamidopropyl di-(heptaetheneoxy) ammonium sulfonate is prepared. This solution is applied to granular polystyrene by soaking the polystyrene granules in the solution for several minutes. The treated granules are then dried. The dried granules contain about 2%, by weight of the polystyrene, of the antistatic agent. The treated granules are molded under heat and pressure into the form of a bar. The molded bar fails to accumulate a static charge of electricity when tested in essentially the same manner described under Example 1. After washing with soap and water, and testing again in' the same manner, it still fails to accumulate a static charge of electricity when repeatedly rubbed with a woolen cloth.

Example 4 Same as in Example 3 with the exception that the nitrogenous compound is gamma-oleamidopropyl dimethyl tetradecaetheneoxy ammonium phosphate, and

Gamma-stearamidopropyl dimethyl tetratriaconessent- 11 1 .2

he d ie e st rsae was ont n sheet L5 b V 17 s lesa etha e-ta se h quaternary. a on um:

we t; o he lyat rsase Qt e s tic sse The alte teetei hlrmi q. q' isl a' u a l li' h ili l molded polystyrene bar'fails to; accumulate static charges geneons com osition and thenpassed through a U. S. of; electricity both before and after washing with soap StandardSieve Series No. 70 screen. The screened prodand water and when tested in essentially the same manner 5 uct'is spray-dried." The iina l prodiict is a fine, free-flowi described under Example 1. V 7 ing powder.

The following examples illustrate the application of V Example 5 nitrogenous compoundsof the kind embraced by Formula Another composition suitable for mold ng P I Q P I to various tektile materials which, .ina' dry state, norrecords is as follows: 10. znally tend to accumulatelstatic charges of enemies.

, Part8 thereon. x T Vinylite VYHH resin 1 Prior to application, 8' x8 sduaresof the desized' h r a ed P I 3 -.--tfabric or cloth to be treated are edged, washed 15 min- Newport-V40 resin utes" infa 0.1% soap and 0.1% soda ash solution at.1 3

Dibasic lead stearate a 15 E, padded and dried 10 minutes in a drying ovenat200 Carbon black --p- F. The cloth 'samplesar'e then placed in sealed vveigh- Min specificallycalctium carbonate ing bottles and weighed. .'.The normal application pro} Gamma -m Ig m P PY hy y y- V cedure comprises boiling the cloth 'sa mples in; fo 'ttie p p l doeicosaetheneoxy ammonium 1111084 most parflsolutions other about 0.1% to about '15 t a ela ig ibfi h ma en! i This chlorinated paraflln wa x is' sold by the Diamond Alkali Company under; the trade name of Chlorowax No.70. It is a 70% chlorinated paraflin'hydrocarbon r This resin 18 sold by Newport Industries, Inc. It is of the type described and claimed in U. S. Patent No. 2,343,845. As described in this patent, the resin is made by reacting a terpene, e. g., turpentine, alpha-pinene or beta-pinene, in the TI} fili z'QQfi 33 p presence of a bforontrifluoride compound at about 3040 6v i ht f the dri d b1 11 bgfG -g and ff jm'p ati' A phonograph record having excellent antistatic charthe afofint of antistatic ag nt r fq iledlby the 'izld tli acteristics is produced by molding thiscomposition'in ac; determined. t 1 t 1 l cordance with thelgeneralpractice followed in producing Statifproperties of. the impregnated cloths are "deter h njd V r 30 rninedirnmedia tely s as removal of the "samples from The following examples illustrate the pretreatment of the-Wei bottles. 'The treated cloths are stroked fillers with an antistatic agent of the kind embraced by with alwoodentdoweland suspended over particles Formula I. The treated filler istthen incorporated info lf QQ a k. The height in inches of the suspefid d, molding compositions such as. described above by way of clqthttoj which no more particles of carbo blaekareat example. Y tracted is Called the antistatic rating If no movement oi Example 6 7 the carbon p articles is observed when the cloth 'i s lie l 'd ippxml ratingofz ero and laundered. The durability or perina- Parts p cent ne cc of antistatic rating is defined as the numberofl Solids a0 launderings to which the treated cloth can be subjected before losing ero static rating. The normal launden, ing procedure employed is similar to the prelirninary laundering and comprises Washing the cloths for 15 min: utes in a {1.1% soap and 0.1% sodaash solution at 135" e in a laboratory agitator washer, followed by thorough The above ingredients are thoroughlyinixed"until a rinsing in water at 135 F. The rinsed samples are then substantially homogeneous composition is obtained, after nipped in a padder, dried 18 minutes at 200 E, and which the mirgture is dried in a steam oven: The'p'rod Weighed to determine the amount of antistatic agent reuct is passed through a U. S Standard Sieve Series No. tained bythe cloth. 20 screen. The resulting finely divided filler has a waxy E l 9 feeling to the touch. a

tactheueoxy ammonium chloride in the form of a soln dissol'vediua mixture of about 40% alcohol and'60% water .Q o. 15 Finely divided calcium carbonate .t l 5 This example illustrates the use of gamma-stearamido- Exam le 7 a pIopy-l dimethyl nonaetheneoxy ammonlum'chloride as Anpum an antistatic agent on a fabric formed of an acrylic fiber, ge t e cent more particularly a fiber which is herein designated as 501155 A-MA fiber and which "is formed of a copolymer of I x about 90-95% acrylonitrile and 10-5% methyl acrylate. teaseassessments:asset Thi ant agent l may be named the P9 anp 0 qlv a ture f ethoxamer (8) of 2-hydroxyethyl gamma-'stearamidoclfrifiii'fifffifliffiflilii fi jjjiiiiii11:12::: i 3;" opy yl mm nium chloride. one method of preparing this compound is described below:

The carbon black and the quaternary ammonium salt (V) V CH3 NEOH are placed in a ball mill and tumbled for about 16 hours. r catalyst The uniform syrup that results is dried in a steam oven. l f g f The dried product is broken up and passed through a 7 0H; 0 U. 3. Standard Sieve Series No. 20 screen. 6:: Example 8 C11Haa-,:C oNH-(onnrNewmomonn, or

A 7 CH2 pprox. p 7 Parts percent M0168 561mg Gammajstearamidopropyl dimethyl Z-hydroxyethyl ammonium chloride (50% solution in iso- Gamma-palrnitamidopropyl dlamyl octadecabute- U neoxy ammonium phosphate the fort of an 7 'P P 464 of 50111 .517. approxin$tellylh'if'isioglqdissogvsdmamixtureof 1 25 Ethylene oxide, 184 g 4.18, eboutgtO a co 0 an weer.

Fjj-lgly diviiaedl g 1 V Sodium hydroxide (catalyst), 5.0 ml. of a 40% 75 aq. .soln 4 I 0.073,

less than /s"v above them, the sample is given a static t a 13 The reaction is carried out in a vessel equipped with a stirrer, a thermometer, an ice-water cooled condenser, and a gas-inlet tube extending below the surface of the liquid. The 184 g. of ethylene oxide is added over a case, 230 g. (5.23 moles) of ethylene oxide is used in-' stead of 184 g. as in Example 9. The 230 g. of ethylene hour period, the temperature varying during this period 5 oxide is added over a 5-hour period, the temperature between 74 and 82 C. A terminal reflux period of varying during this period between 73 C. and 82 C. 1 /2 hours is allowed to insure completeness of the reac- A terminal reflux period of 2 hours is allowed to insure tion. The solution is filtered, neutralized to a pH of 7.0 completeness of the reaction. The weight of the final with dilute hydrochloric acid solution, and evaporated on reaction mass is 481 g. It is a thin, reddish syrup that a steam bath. The residue is dried for several days in is soluble in water. vacuo over sulfuric acid. The product is obtained in a A 5% solution of the above compound (solids basis) Yield of 431 is applied to a fabric formed of A-MA fiber, using an Various concentrations of the above compound in 80:1 liquor-to-cloth ratio. The treated fabric has ex- Watel' are pp to fabric formed of fiber cellent antistatic properties which it retains after at least lowing the general procedure hereinbefore described. In 5 laundefings Th ti t d t are given in Tabl 11. all cases the treated fabric has excellent antistatic properties through more than 5 soap and soda ash launder- Example 12 ings. The pertinent data are given in Table 1. Same as in Example 11 with the exception that the TABLE I Treated cloth Antistatie Before After 1 After 5 Bath con- Liquid rating laundering laundering launderings centration, to Cloth of unpereent cloth oftreated solids ratio cloth Percent Anti- Percent Anti- Percent Antiin finish static finish static finish static inches on rating on rating on rating cloth in cloth in cloth in inches inches inches 0.1 40:1 A-MA 2% 3.5 0 3.1 0 3.2 0 0.25 40:1 A-MA 2% 4.2 0 3.9 0 3.0 0 0.4 40:1 A-MA 2% 4.6 0 4.2 0 3.6 0 5.0 80:1 A-MA 2% 10.3 0 5.7 0 4.6 0

Example 10 antistatic agent employed is gamma-stearamidopropyl This example illustrates the use of gamma-stearamidodlmethyl hexadecaetheneoxy ammomum chlonde Whlch propyl dimethyl hexaetheneoxy ammonium chloride as also may be named s thepolyethoxamer (15) of 2 hyan antistatic agent on a fabric formed of A-MA fiber. dmxyethyl gamma'stearamldopropyl dmethly ammomum This quaternary ammonium compound also may be chlofldeone method of Preparing this mmpound is named as the polyethoxamer (5) of 2-hydroxyethyl gam- 40 described below: ma-stearamidopropyl dimethyl ammonium chloride, The reactants and the general procedure are essentially One method of preparing this compound is described bethe same as in Example 9 with the exception that, in low: this case, 341 g. (7.75 moles) of ethylene oxide is used M0168 instead of 184 g. as in Example 9. The 341 g. of ethylene -s p p py .dlmefllyl YQ 'Q Y oxide is added over a 5 /2 hour period, the temperature ethyl ammomum chlonde (59% 501mm 111 varying during this period between 73 C. and 81 C. p g f i 2 of 50111 32 A terminal reflux period of 2 hours is allowed as in g i g i g g g 0'O73 Example 11. The Weight of the final reaction mass is y 600 g. It is a thin, light-brown syrup which is soluble To the isopropanohc solution of the quaternary ami watel; monium salt is added 5.0 ml. of 40% aqueous solution A 71 aqueous l i f h above compound of sodium hydroxide- 123 of ethylene oxide 15 (solids basis) is applied to a fabric formed of A-MA f l over a hour f lhe tfmpgramre dufmg fiber, using an 80:1 liquor-to-cloth ratio. The treated this time ,Vanes between, 71 and 83 f f fabric has excellent antistatic properties which it retains reflux period of 2 hours is allowed. Thesolutron 1s tnen after at least 5 launderings The pertinent data are filtered, neutralized to a pH of 7.0 with hydrochloric T H H acid, evaporated on a steam bath, and the product dried gwen m a e in vacuo over sulfuric acid. The product is a very soft, Example 13 light-brown paste. The yield is 367 g. (theoretical yield, 35 g), This example illustrates the use of gamma-stearamido- A 5% aqueous solution of the above compound is appropyl dimethyl heneicosaetheneoxy ammonium chloride plied to a fabric formed of AMA fiber, using an 80:1 as an antistatic agent on a fabric formed of A-MA fiber. liquor-to-cloth ratio. The treated fabric has excellent Thi quaternary m nium compound also may be antistatic properties which it retains after at least 5 named as the polyethoxamer 20) of zh d h l launderings. The pertinent data are g1ven in Table II. gamma stearamidopmpyl i h l ammonium h1 id Example 11 One method of preparing this compound is described This example illustrates the use of gamma-stearamidobelow' propyl dimethyl undecaetheneoxy ammonium chloride as Moles an antistatic agent on a fabric formed of A-MA fiber. Ga tearamidopropyl dimethyl Z-hydroxyeth- This quaternary ammonium compound also may be yl ammonium chloride (50% solution in isopronamed as the polyethoxamer (10) of Z-hydroxyethyl panol), 406 g. of soln 0.452 gamma-stearamidopropyl dimethyl ammonium chloride. Ethylene oxide, 401 g 9.12 One method of preparing this compound is described be- Sodium hydroxide (catalyst), 80ml. of a 40% aq. low: soln. 0.117

The. Pro edu e s essen a l sams. as tha dssse b enshrined; .01; a f e yl ne a added xe a or qi r. t d e he em eratu e an d rin period between 71 'C, and 82,50. A terminal reflux e od O a qwed q nsur om eti n f the reaction. 'The weight of the final-reaction mass is. It s a h n eddish. y uoti 2 a eou so i n 9 hr cg s'e s l nt antis a err re t s wh it e a n eTa ls e evqsemn f (seli sba s. e nl sd br rmed of iA-MA fiber, 'using an 8011' liquor-to-cloth ratio. 1ThfilftQ 'Gamma-sicaramidopropyldimethyl Z-hydroxyQethylasses-. 31

TABLE'IIL Tr ated cl th.

.Anti- Bath static conrating Beiore After l Afterfi After 10. cenof laundering 'launglering laundermgs launderings tra un. V a 7 4 l, e r '1 e -per-' A-MA Per Anti- Per- Anti Rer- Antr- Per- Anticent cloth cent static cent static cent static cent static Solids n s t n" fin sh refine ni rating fi is in inches on in I on in Y on in on in cloth in h cloth inches cloth inches cloth inches 0.3 2% 4.7 0 3.7 0 3.6 O 3.8 0.4L--- 2% 5.1 0 4.1 0 s 3.8 0v 3 0 2.0-..- p 2% 7. 3 0. 5, 1 0. 3. 6 0 3. 7

Examplel5 monium chloride. v 'One of preparing this come TA LE V V Treated cloth 7 Anti: n

static Solution of rating Before After 1 After 5 antistatic oiunlaundering laundering launderings...

agent of treated example cloth of A-MA Percent Anti- Percent Anti- Percent Anti,-

fiberin finish static finish static finish static inches on rating on rating on rating cloth in cloth in cloth fin inches inches 7 inches Example 14 Moles Gammarstearamidopropyl dimethyl Z-hydroxyethyl mm m l ide 0% s l on in i5 7. propanol), 112 g. of soln 0.125

Sodium hydroxide (catalyst), 12.5- ml. of 40% aq.

spirit- M 0.18

Initially, 5.0 ml. of a 40% aqueous solution of, sodium hydroxide is employed as a catalyst. The addition of all of the ethylene oxide is carried outover. a prolonged period as described in the previous examples. The in troduction of further amounts of catalyst from time to.

time is found to be necessary, perhaps because of the, presence of some ethylene chlorohydrin in this particular solution of quaternary ammonium salt. The weight of the final product. is 269. g., indicating that 25 equivalents of; ethylene oxide has reacted. A portion (A) of the All Same as in Example -14 with the exception that. the 7' antistatic agent employed is gammastearamidopropyl dimethyl dopentacontaetheneoxy ammonium chloride, which also may be named as thepolyethoxamer (52) ot Z-hydr yethyl gamma-stearamidopropyl dimethyl ampound is described, below:

" ammonium chloride (%g'solution in isopro 'added'over' a" period o f"11 /2 hours, the temperature. varying during this period between 81 and 97 C. A mi a efl x Pe d f 3 i nute i a owe to n u o n et uo the rea on e We ht of't fi a e ti n m s s 9v s i d ca i a 52.. eq v n of thy e e i e s r a ted- A qu l ion. the abo e anfist ti agent (s l basis) is pp ied abri f med fA-MA fi e Solution is neutralized to. a pH of 3. with hydrochloric acid. The remainder of the. solution is. reacted with more ethylene oxide to, form a higher-molecular-Weight prod c Q Various conccntrationsinwater of-portiou (A) of the solution of gamma-stearamidopropyl dimethyl pentacosa etheneoxy ammonium chloride are applied .to fabric formed oi fiber following the generalprocedure ee eal-arm use? than-awn an f; 9 h ll ases. the rea ed. fa ri has excellent an is c nrcne ticsfllrough more than 5 soa and soda ash launderings. The pertinent. data are given in Table III. N a I using a 402i liquor-to-cloth ratio. The treated, fabric has excellent antistatic properties which it retains after at least 5 launderings. Table IV. V 7

Example, 16

This example illustrates the use of gamma-steararnidopropyl dimcthyl decaetheneoxyTammonium 'dihydiogenphosphate as an an'tistatica'gent o'ii'a "fabricform'edof A- MA fiber. This quaternary ammonium compound also may be named polyethoxainer (10)" of 2-hydroxyethyl gamma-stearamidopropyl dimethyl ammonium dihydrogcn phosphate. One method ofpreparing'thi's'compound is described below: i a

' Moles Gamma-stearamidopropyl dimethyl Z-hydroxy-ethyl ammonium dihydrogen phosphate (as an 'a'quc' ous isopropanolic solution containing 36%" active solids), 7142 g. of soln 0.10 Ethylene oxide, 107 g. V 2.43 Sodium hydroxide (catalyst); 0;s f f 0,015

To the aQHeOHSriSOPIOPHIIOliC solution of the quaternary ammonium salt is added 1.05 ml. of a 40% aqueous.

solution of sodium hydroxide (15 mole percent. based on the quaternary salt), and the mixture is heated to reflux on a steam bath. The reaction is carried out in a reaction vessel fitted with a stirrer, a thermometer, a

Dry-Ice condenser; and'a gas-inlet'tube leadingbeneath.

the surface of the liquid. *Ethiylene oxide is introduced into the hot solution at such'a rate that a moderate reflux is obtained. The temperature is held between 82 and 89 C. throughout the""10 7a hoof addition period by'heating the vessel andcon'tents on'a steam bath A terminal reflux period (temperature to 93 C.) of 3 hours The pertinent data are given in I17 is allowed to insure completeness of the reaction. The Weight of the resulting solution containing 51% solids is 191 g., indicating that 10 equivalents of ethylene oxide has reacted. The solution is neutralized to a pH of 6 by the addition of 85% phosphoric acid.

Aqueous solutions of the above compound, in bath concentrations of 0.5% and 1% (solids basis), are separately applied to fabric formed of AMA fiber, using a 40:1 liquor-to-cloth ratio. The treated fabric has excellent antistatic properties which it retains after at least 5 launderings. The pertinent data are given in Table IV.

TABLE IV Anti- Treated cloth static rating Solution of un- Before After 1 After-'3 of antitreated laundering laundering launderings static cloth agent of of v example A-MA Per- Anti-" "Per-i Anti- Per- Antifiber: cent static. cent static .cent static in finish rating finish rating finish ratinginches on in on in on in cloth inches cloth inches cloth inches 15 2% 4.5 3.3 0 3.3 0 16 2% 4. 6 0 3. 6 0 3. 2 0 16 2% 5.5 0 3.6 t 0 3.5 0

- 0.4% concentration (solids basis) of antistatic agent in application bath. b 1%.57 concentration (solids basis) of antistatic agent in application I 21.11% concentration (solids basis) of antistatic agent in application Example 17 This example illustrates the use of gamma-lauramidopropyl dimethyl pentadecaetheneoxy ammonium chloride as an antistatic agent on a fabric formed of A-MA fiber. This antistatic agent also may be named as the polyethoxamer (14) of Z-hydroxyethyl gamma lauramidopropyl dimethyl ammonium chloride. preparing this compound is described below:

The gamma-lauramidopropyl dimethyl amine is dissolved in an equal weight of isopropanol and 6.25 ml. of 12 N hydrochloric acid (75% of the theoretical quantity) added. The mixture is placed in a 300 ml. three-necked flask equipped with a mechanical stirrer, a thermometer, a Dry-Ice reflux condenser, and a gas-inlet tube extending below the surface of the liquid. To the solution is added 5.0 ml. of water, and the mixture is heated on a steam bath to reflux. At this point, the addition of ethylene oxide is initiated and then continued at such a rate that a gentle reflux is maintained. The addition of all 72.0 g. of ethylene oxide requires four hours. The temperature is held at 8893 C. during this period by heating on a steam bath. An additional half-hour interval of reflux (temperature to 96 C.) is allowed to One method of cloth ratio of 40:1. In one instance the fabric of A-MA 'i 18 insure that the reaction is complete. The weight of the final product of 73% solids is 134 g., indicating that fifteen equivalents of ethylene oxide has reacted. The solution is then adjusted to pH 3 by the addition of 2-3 ml. of 12 N hydrochloric acid.

Aqueous solutions of the above compound are applied to fabric formed of A-MA fiber following the general procedure hereinbefore described. An application-bath concentration of 0.5% antistatic agent (solids basis) is used in one instance and of 1% (solids basis) in another case. In both tests the treated fabric retains a positive antistatic characteristic after being subjected to one soap and soda ash laundering.

Example 18 Moles Gamma-stearamidopropyl'dimethyl amine, 36.8 g 0.10 Ethylene oxide, 56.0 g 1.27 Hydrochloric acid (75% added initially; the remaining 25% finally), 8.34 ml. of 12 N aq. soln 0.10

The procedure is essentially the same as that described under Example 17. The addition of all 56 g. of ethylene oxide requires. 2 hours, the temperature ranging between 75 C. and 94 C. during this period. A terminal reflux period of 3 hours is used in order to insure completeness of the reaction. The weight of the final reaction mass is 128 g., indicating that 9 equivalents of ethylene oxide has reacted.

Following the general procedure hereinbefore described, the above compound is applied to fabrics comprised of the following fibers: Acrilan, Dacron, Dynel, Orlon and nylon (all of which are commercially available) and A-MA fiber. On all of these fibers the antistatic agent is applied from an application bath containing about 1% (solids basis) of the antistatic agent, and using a liquid-tofiber is treated with a 0.5% concentration (solids basis) of the antistatic agent in the application bath. In the case of the fabric comprised of the A-MA fiber, a durable antistatic rating is obtained through more than 5 launderings. A degree of substantivity is noted on the fabric formed or: Orlon, but there is no substantial increase in antistatic durability. The treatedfabrics comprised of Acrilan, Dacron, Dynel, Orlon and nylon fibers all show good antistatic properties initially, but tend to lose this characteristic upon laundering. The pertinent data are given in Table V.

TABLE V Anti- Treated cloth static 60 rating of un- Before After 1 After 5 treated laundering laundering launderings Cloth ofcloth in inches Per- Anti- Per- Anti- Per- Anticent static cent static cent static finish rating finish rating finish rating 3 on in on in on in cloth inches cloth inches cloth inches A-MA 2% 4. 4 0 3. 8 0 A-MA 2 /5 5. 2 0 4. l 0 Acrllan. 2% 0. 8 0 0 1 Dacron 2% 0.9 0 0 2 Dynel 2 0.6 0 0 2 Orlon 2 1.9 0 1.3 0 Nylon 2% 0. 7 0 0 2 b 23.5% concentration (solids basis) of antistatic agent in application a 7 2,11% concentration (solids basis) of antistatic agent in application a -19 Example 19 This example. illustrates the use, as an antistatic agent on 'the same fabrics treated in Example 19, of a mixture of about 50% of gamma-stearamidopropyl tri-(dodecaetheneoxy) ammonium chloride and about 50% of gammarstearamidopropyl di(dodecaetheneoxy) ammonium chloride. One 'method of preparing this mixture is described below:

v11) CiiHanC ONHKCHDa-hl Moles Gammastearamidopro'pyl bis (2 hydroxyethyl) amine, 64.3 g Eethylene oxide, 189.0 g Hydrochloric acid (65% of the theoretical amount),

g. of 12 N acid 0.098

The amine is dissolved in 64 g. of sec.-butanol, the acid added, and the solution heated to 104 C. The entire amount of ethylene oxide is then added over a period of 9 hours and at a reaction temperature of '85-98 C. A 5-minute terminal period 'of reflux at 105 C. is allowed. The weight of the resulting reaction mass is 315 "g., indicating that 185 g; (4.2 moles, 28 equivalents) of ethylene oxide has reacted. A titration curve possessed two brakes, from which it is postulated that the reaction mixture contains the'following two products in approximately equal amounts:

(VIII) (om'oniomn 011E350ONH(C-Hi);-(CHCH1O)1:H, or-

and

The reaction mixture is adjusted to a pH of S with hydrochloric acid.

A solution of the mixture of nitrogenous compounds produced as described above is applied to fabrics com 7 fiber, adurable antistatic rating is obtained through morethan 5 'launderings. A degree of substantivity is noted on the fabric formed of' Orlon, but there is no substantial increase in antistatic durability. The treated fabrics comprised of *Acrilan, Dacron, Dynel, Orion and nylon fibe'rs all show good antistatic properties initially, but tend to lose this characteristic uponlaundering;

, The pertinent data are given in Table VI.

' TABLEVI V Treated cloth Antiv V static Before 7 Aiterl I Aiter 5 7 rating laundering laundering iaundcrmgs Cl0t-hofofunr treated cloth in Percent Anti- Percent Anti- Percent Antiinches finish static finish static finish static on rating on rating on rating cloth in cloth in cloth in inches inches inches AMA.. 2% 6. 4 0 3. 8 Acrilan.- 2% 2.1 0 0 Dacron... 2% 2.1 0 v 0 Dyue1.--- 2 2.2 0 O Orlon 2 3.7 '0 2.1 Nylon"... 2% 1.9 0 0 Example 20 .Example 16 is repeated but substituting for, cloth formed of A-MA fiber, employed in that example, the following: g 7

Silk cloth Woolen flannel Rayon suiting Rayon challis Acetate rayon fabric The treated fabrics fail to accumulate static charges of electricity when stroked with metal, glass or plastic combs whereas the untreated fabrics rapidly pickup and retain electrostatic charges when subjected to these same tests.

It will be understood, of course, by those skilled in the art that the present invention is not limited to the particular compositions containing the particular ingredients and proportions thereof thatare given in the above illustrative examples. Examples of other molding compositions which can be modified by incorporating therein an antistatic agent'comprising a nitrogenous compound of the kind embraced by Formula I are those disclosed and claimed in, for instance, U. S. Patents 2,572,798, 2,616,- 862 and 2,636,869, as well as others directed to the production of sound records. Nitrogenous compounds other than those given in the foregoing examples and which are embraced by Formula I also can be used in lieu of or conjointly with the specific nitrogenous compound named in the particular example.

We claim:

1. A water-insoluble, organic article which in a dry;

state normally has a tendency to accumulate static charges of electricity thereon, said article having deposited at least on outer surfaces thereof an antistatic composition comprising a quaternary ammonium compound represented by the general formula andradicals having the same, meaningas R, R rep resents a memberiofzthe group. consisting of hydrogenand'radicals having jthe same meaning asR", and Y represents 'an anion, the amount of the said quaternary ammonium compound Which jis associatedwith thesaid article corresponding to from 0.2% to 157% of the weight of the dry, untreated 'article,.'and said quaternary ammonium compound lessening .the tendency of the said article to accumulate Jstatic charges of electricity thereon. -2. A water-insoluble, organic, article as in claim 1 '21. wherein Y in the general formula for the quaternary ammonium compound represents a chloride.

3. A water-insoluble, organic article as in claim 1 wherein Y in the general formula for the quaternary ammonium compound represents a phosphate.

4. A water-insoluble, organic article as in claim 1 wherein m in the formula for the radical represented by R in the general formula for the quaternary ammonium compound represents a positive integer from 6 to 60, inclusive.

5. A water-insoluble, organic article as in claim 1 wherein the quaternary ammonium compound is stearamidopropyl dimethyl nonaetheneoxy ammonium chloride.

6. A water-insoluble, organic article as in claim 1 wherein the quaternary ammonium compound is stearamidopropyl dimethyl pentacosaethen'eoxy ammonium chloride.

7. A water-insoluble, organic article as in claim 1 wherein the quaternary ammonium compound is a mixture of stearamidopropyl di-(dodecaetheneoxy) ammonium chloride and stearamidopropyl tri-(dodecaetheneoxy) ammonium chloride.

8. A water-insoluble, organic article as in claim 1 wherein the quaternary ammonium compound is stearamidopropyl dimethyl decaetheneoxy ammonium phosphate.

9. A shaped, water-insoluble, organic article comprising a water-insoluble vinyl resin which in a dry state normally has a tendency to accumulate static charges of electricity thereon, said article having deposited at least on outer surfaces thereof an antistatic composition comprising a quaternary ammonium compound represented by the general formula wherein R represents a member of the group consisting of aliphatic hydrocarbon and alicyclic hydrocarbon radicals containing at least 7 carbon atoms, R designates a radical represented by the formula -(C,,H ,,O),,,H where n represents a positive integer from 2 to 4, inclusive, and m is a positive integer and is at least 6, R represents a member of the group consisting of alkyl and hydroxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and radicals having the same meaning as R, R represents a member of the group consisting of hydrogen and radicals having the same meaning as R", and Y represents an anion, the amount of the said quaternary ammonium compound which is associated with the said article corresponding to from 0.2% to of the weight of the dry, untreated article, and said quaternary ammonium compound lessening the tendency of the said article to accumulate static charges of electricity thereon.

10. A textile formed of fibers including water-insoluble, organic fibers of a thermoplastic product of polymerization of polymerizable vinyl compound including acrylonitrile, said textile in a dry state normally having a tendency to accumulate static charges of electricity thereon and, to lessen this tendency, having deposited at least on outer surfaces thereof an antistatic composition comprising a quaternary ammonium compound represented by the general formula wherein R represents a member of the group consisting of aliphatic hydrocarbon and alicyclic hydrocarbon radicals containing at least 7 carbon atoms, R designates a radical represented by the formula (C,,H ,,O) H where n represents a positive integer from 2 to 4, inclusive, and m is a positive integer and is at least 6, R" represents a member of the group consisting of alkyl and hydroxyalkyl radi- '22 cals containing from 1 to 5 carbon atoms, inclusive, and radicals having the same meaning as R, R' represents a member of the group consisting of hydrogen and radicals having the same meaning as R", and Y represents an anion, the amount of the said quaternary ammonium compound which is associated with the said textile corresponding to from 0.2% to 15% of the weight of the dry, untreated textile, and said quaternary ammonium compound lessening the tendency of the said textile to accumulate static charges of electricity thereon.

11. A molding composition comprising (1) a waterinsoluble, organic plastic material which normally tends to accumulate static charges of electricity after the article has been molded and (2) anantistatic agent therefor comprising a quaternary ammonium compound represented by the general formula wherein R repersents a member of the group consisting of aliphatic hydrocarbon and alicyclic hydrocarbon radicals containing at least 7 carbon atoms, R designates a radical represented by the formula -(C H O) H where n represents a positive integer from 2 to 4, inclusive, and m is a positive integer and is at least 6, R" represents a member of the group consisting of alkyl and hydroxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and radicals having the same meaning as R, R' represents a member of the group consisting of hydrogen and radicals having the same meaning as R, and Y represents an anion, the amount of the said quaternary ammonium compound which is in corporated in the said molding composition constituting, by weight, from 1% to 15% of the weight of the said plastic material.

12. A product comprising the molded composition of claim 11.

13. The method of conditioning a water-insoluble, organic material which, in a dry state, normally tends to accumulate static charges of electricity thereon, said method comprising applying to the said material a volatile liquid containing a quaternary ammonium compound represented by the general formula wherein R represents a member of the group consisting of aliphatic hydrocarbon and alicyclic hydrocarbon radicals containing at least 7 carbon atoms, R designates a radical represented by the formula --(C,,H 0) H where n represents a positive integer fiom 2 to 4, inclusive, and m is a positive integer and is at least 6, R" represents a member of the group consisting of alkyl and hydroxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and radicals having the same meaning as R, R represents a member of the group consisting of hydrogen and radicals having the same meaning as R", and Y represents an anion, and the amount of the said liquid containing the said quaternary ammonium compound which is applied to the said material being such that the finished material has associated therewith from, by weight, 0.2% to 15% of the said quaternary ammonium compound, based on the weight of the dry, untreated material, and drying the thus treated material.

14. A method as in claim 13 wherein the water-insoluble, organic material which is conditioned is a shaped, water-insoluble, organic article comprising a water-insoluble vinyl resin which in a dry state normally tends to accumulate static charges of electricity.

15. A method as in claim 13 wherein the water-in soluble, organic material which is conditioned is a textile formed of fibers including water-insoluble, organic fibers 76 of a thermoplastic product of polymerization of polymer izable vinyl'compound including acrylonitrile said tex:

tile in a dry state normally having a tendency to accumulate static charges of electricity themon. j 1 V 16. The method which comprises incorporating an anti static-agent into a moldings-composition containing a water-insoluble, organic plastic material which normally tends to accumulate-static charges of electricity after the articlehas been molded, said antistatic agent comprising a quaternary ammonium compound represented by the It represents a positive integer from 2 to 4, inclusive, and

m is a positive integer and'is atlcast 6, 11" represents a member of the group consisting of alkyl and hydroxyalkyl radicals containing from xl to 5 carbon atoms, inclusive,

and radicals having the same meaningas RQI'R represents a member of thegroup consisting ofhydrogen and radicals having thejsa-me meaning asR", and Y represents an anion, the amount of the'sajd quaternary ammonium compound which is incorporated in the said molding composition being, by weight, from 1% to 15% of the weight of the said plastic material,- and moldin the resulting molding composition.

References Cited in the file of thispatent UNITED STATES PATENTS UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. y 3 y5 V May 2'7, 1958 Arnold. Gruber et a1,

It .is hereby certified that error appearm in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 60 after "decenyl" insert a comma; line 69, after "radicals" insert a comma; celumn 2 line! 4, after thiocysnate" insert a comma; line 5, after "acetate insert a comma; column A, line 15, for "alyklene" read as alkylene line 41 for "diabasic" read as dibasic line 46; for "ethlene" read ethylene column 7,. line 30, strike out "The antistatic compositions involved herein have been" and insert the same before "found" in line 32 same column; column 8, line 54, for "characterisitcs read characteristics s; column 10, line 52, Example 2, in the table, first column thereof, fifth item for "We .ght" read me weight e; column 14, line 38 for "dimethly" read dimethyl ==-=i column 19 line 41, for "brakes" read =e breaks column 22, line 21 for "repersents read. represents Signed and sealed this 16th day of September SL958a (SEAL) Attest: I I I KARL Ii, AXLINE ROBERT Go WATSON Attesting Officer Commissioner of Patents 

1. A WATER-INSOLUBLE, ORGANIC ARTICLE WHICH IN A DRY STATE NORMALLY HAS A TENDENCY TO ACCUMULATE STATIC CHARGES OF ELECTRICITY THEREON, SAID ARTICLE HAVING DEPOSITED AT LEAST ON OUTER SURFACES THEREOF AN ANTISTATIC COMPOSITION COMPRISING A QUATERNARY AMMONIUM COMPOUND REPRESENTED BY THE GENERAL FORMULA 